KR102339004B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification provides a compound of Formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device including the same

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2019-0007477 filed with the Korean Intellectual Property Office on January 21, 2019, the entire contents of which are incorporated herein by reference.

The present application relates to a compound and an organic light emitting device including the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including a first electrode and a second electrode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the first electrode and electrons are injected into the organic material layer at the second electrode, and excitons are formed when the injected holes and electrons meet. , when this exciton falls back to the ground state, it glows.

The development of new materials for the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2011-0107681

An object of the present application is to provide a compound and an organic light emitting device including the same.

The present application provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1 to R4 are each independently hydrogen; or deuterium,

R5 and R6 are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a is an integer from 0 to 6,

b and d are each independently an integer of 0 to 4,

c is an integer from 0 to 2,

a to d are each independently, when 2 or more, the substituents in parentheses are the same as or different from each other,

b to d are each independently, and when two or more, two or more R2 to R4 are each independently adjacent substituents may be bonded to each other to form a ring.

In addition, the present application is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound described above.

The organic light emitting device using the compound according to the exemplary embodiment of the present application can have a low driving voltage, high luminous efficiency, or a long lifespan.

1 illustrates an example of an organic light emitting device in which a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked.
2 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), electron injection and An example of an organic light emitting device in which the transport layer 9 and the second electrode 4 are sequentially stacked is shown.

Hereinafter, the present specification will be described in more detail.

The present specification provides a compound represented by Formula 1 above.

According to an exemplary embodiment of the present application, the compound represented by Formula 1 has the above-described core structure, and thus has the advantage of controlling triplet energy, and can exhibit long life and high efficiency characteristics.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" includes hydrogen; halogen group; nitrile group; nitro group; hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto. does not

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10-C24. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

,

,

및

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

and

and the like, but is not limited thereto.

In the present specification, the heterocyclic group includes at least one atom or a heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. Although the number of carbon atoms of the heterocyclic group is not particularly limited, it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.

In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; In the N-alkylheteroarylamine group and the heteroarylamine group, the description of the alkyl group, the aryl group and the heteroaryl group described above may be applied to the alkyl group, the aryl group and the heteroaryl group, respectively.

As used herein, "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present specification, the meaning of adjacent groups combining with each other to form a ring means that adjacent groups combine with each other as described above to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle, and monocyclic Or it may form a polycyclic ring, and may be in an aliphatic, aromatic or condensed form thereof, but is not limited thereto.

In the present specification, the meaning of forming a ring by bonding with adjacent groups means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with adjacent groups; A substituted or unsubstituted aromatic hydrocarbon ring; substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; Or it means that they form a combined form.

In the present specification, the aliphatic hydrocarbon ring is a non-aromatic ring and refers to a ring consisting only of carbon and hydrogen atoms.

In the present specification, the description of the aryl group described above may be applied, except that the aromatic hydrocarbon ring is a divalent group. Examples of the aromatic hydrocarbon ring include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, and the like.

In the present specification, the description of the above-mentioned heterocyclic group may be applied, except that the heterocyclic group is a divalent group.

In the present specification, the aliphatic heterocycle refers to an aliphatic ring including one or more heteroatoms.

In the present specification, the aromatic heterocycle refers to an aromatic ring including one or more heteroatoms.

The compound represented by Formula 1 is selected from any one of Formulas 2 to 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, R1 to R6 and a to d are as defined in Formula 1.

According to an exemplary embodiment of the present application, R1 to R4 are each independently hydrogen; or deuterium.

According to an exemplary embodiment of the present application, R1 to R4 are hydrogen.

According to an exemplary embodiment of the present application, when b to d are each independently 2 or more, two or more R2 to R4 may each independently combine adjacent groups to form a ring.

According to an exemplary embodiment of the present application, when b is 2 or more, two or more R 2 may combine adjacent groups to form a ring.

According to an exemplary embodiment of the present application, when b is 2 or more, two or more R 2 may combine adjacent groups to form a benzene ring.

According to an exemplary embodiment of the present application, when c is 2 or more, two or more R 3 may combine adjacent groups to form a ring.

According to an exemplary embodiment of the present application, when c is 2 or more, two or more R 3 may combine adjacent groups to form a benzene ring.

According to an exemplary embodiment of the present application, when d is 2 or more, two or more R 4 may combine adjacent groups to form a ring.

According to an exemplary embodiment of the present application, when d is 2 or more, two or more R 4 may combine adjacent groups to form a benzene ring.

The compound represented by Formula 1 is selected from any one of Formulas 2-1 to 2-8, 3-1 to 3-8, and 4-1 to 4-8.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

In Formulas 2-1 to 2-8, 3-1 to 3-8, and 4-1 to 4-8, R4 to R6 and d are as defined in Formula 1,

R7 and R8 are each independently hydrogen; or deuterium,

e1 and e2 are each 0 or 1, the sum of e1 and e2 is 1 to 2,

e is an integer from 0 to 10, f is an integer from 0 to 8,

When e is 2 or more, a plurality of R7 are the same as or different from each other,

When f is 2 or more, a plurality of R8s are the same as or different from each other.

According to an exemplary embodiment of the present application, R5 and R6 are each independently, a substituted or unsubstituted C6-C60 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to an exemplary embodiment of the present application, R5 and R6 are each independently, a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present application, R5 and R6 are each independently a substituted or unsubstituted C6-C15 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.

According to an exemplary embodiment of the present application, R5 and R6 are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted phenanthrene group; a substituted or unsubstituted carbazole group; a substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofuran group.

According to an exemplary embodiment of the present application, R5 and R6 are each independently a phenyl group; naphthyl group; biphenyl group; phenanthrene group; a carbazole group unsubstituted or substituted with a phenyl group; dibenzothiophene group; or a dibenzofuran group.

In addition, according to an exemplary embodiment of the present specification, the compound represented by Formula 1 is any one selected from the following structural formulas.

In addition, the present specification provides an organic light emitting device including the above-described compound.

In one embodiment of the present specification, the first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In the exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the compound.

In an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the compound as a host.

In an exemplary embodiment of the present specification, the organic material layer includes an emission layer, the emission layer includes the compound of Formula 1 as a first host, and further includes a second host represented by Formula H below.

[Formula H]

In the above formula (H),

A is a substituted or unsubstituted naphthalene ring,

Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,

L1 to L3 are each independently, a single bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,

Ar2 and Ar3 are each independently, a substituted or unsubstituted C6-C60 aryl group; Or a C 2 to C 60 heteroaryl group containing at least one heteroatom among substituted or unsubstituted N, O and S,

p is an integer from 0 to 9;

In an exemplary embodiment of the present specification, A is a substituted or unsubstituted naphthalene ring.

In an exemplary embodiment of the present specification, A is a naphthalene ring unsubstituted or substituted with deuterium.

In one embodiment of the present specification, A is a naphthalene ring.

In the exemplary embodiment of the present specification, p means the number of substitutions of deuterium, and when p is 0, it means a state in which all of them are substituted with hydrogen.

In one embodiment of the present specification, L1 to L3 are each independently, a single bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 to L3 are each independently, a single bond; a substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthalene group.

In one embodiment of the present specification, L1 to L3 are each independently, a single bond; a phenylene group unsubstituted or substituted with deuterium; Or a naphthalene group unsubstituted or substituted with deuterium.

In one embodiment of the present specification, L1 to L3 are each independently, a single bond; phenylene group; or a naphthalene group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted C6-C30 aryl group.

In an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; or a substituted or unsubstituted naphthyl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group; a biphenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group; a terphenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group; or a naphthyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group; biphenyl group; terphenyl group; or a naphthyl group.

In an exemplary embodiment of the present specification, Ar1 is a phenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, a tertbutyl group, an adamantyl group, a phenyl group and a naphthyl group; biphenyl group; terphenyl group; or a naphthyl group.

In an exemplary embodiment of the present specification, Ar2 and Ar3 are each independently, a substituted or unsubstituted C6-C30 aryl group; or a C 2 to C 30 heteroaryl group including at least one heteroatom among substituted or unsubstituted N, O and S.

In an exemplary embodiment of the present specification, Ar2 and Ar3 are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group.

In an exemplary embodiment of the present specification, Ar2 and Ar3 are each independently a phenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, an alkyl group, a cycloalkyl group, and an aryl group; a biphenyl group unsubstituted or substituted with deuterium; a terphenyl group unsubstituted or substituted with deuterium; a naphthyl group unsubstituted or substituted with deuterium; a fluorenyl group unsubstituted or substituted with an alkyl group; a dibenzofuranyl group unsubstituted or substituted with deuterium; Or a dibenzothiophenyl group unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present specification, Ar2 and Ar3 are each independently a phenyl group unsubstituted or substituted with a group selected from the group consisting of deuterium, a tertbutyl group, an ammantyl group, and a phenyl group; biphenyl group; terphenyl group; naphthyl group; dimethyl fluorenyl group; dibenzofuranyl group; or a dibenzothiophenyl group.

In an exemplary embodiment of the present specification, the second host represented by Formula H may be represented by any one of the following structures, but is not limited thereto.

In the exemplary embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.

In an exemplary embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. It further includes one or more layers selected from the group consisting of an electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

In an exemplary embodiment of the present application, the organic light emitting device includes a first electrode; a second electrode provided to face the first electrode; and a light emitting layer provided between the first electrode and the second electrode. and two or more organic material layers provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, and at least one of the two or more organic material layers includes the compound. In an exemplary embodiment of the present application, two or more organic material layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer for simultaneously transporting electrons and electron injection, and a hole blocking layer.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a second electrode, one or more organic material layers, and a first electrode are sequentially stacked on a substrate.

The organic light emitting device may have, for example, a stacked structure as follows, but is not limited thereto.

(1) anode/hole transport layer/light emitting layer/cathode

(2) anode / hole injection layer / hole transport layer / light emitting layer / cathode

(3) anode/hole transport layer/light emitting layer/electron transport layer/cathode

(4) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(5) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode

(6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(7) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode

(8) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(9) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode

(10) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(11) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(12) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(13) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(14) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(15) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(16) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport and injection layer / cathode

For example, the structure of the organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2 .

1 illustrates a structure of an organic light emitting device in which a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked. In such a structure, the compound may be included in the light emitting layer 3 .

2 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), electron injection and The structure of the organic light emitting device in which the transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. In this structure, the compound is the hole injection layer (5), the hole transport layer (6), the electron blocking layer (7), the light emitting layer (3), the hole blocking layer (8), and the electron injection and transport layer (9) It can be included on the first floor or more. In such a structure, the compound may be included in the light emitting layer 3 .

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of the present specification, that is, the compound.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Formula 1 above.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on a substrate to deposit the first electrode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a second electrode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing the second electrode material, the organic material layer, and the first electrode material on the substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a first electrode material on a substrate from the second electrode material (International Patent Application Laid-Open No. 2003/012890). However, the manufacturing method is not limited thereto.

In the exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

As the material for the first electrode, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the first electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The second electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the second electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes and has a hole injection effect in the first electrode, an excellent hole injection effect for the light emitting layer or the light emitting material, and in the light emitting layer A compound that prevents the generated exciton from moving to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the first electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the first electrode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. Mobility for holes This large material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electronic blocking layer may be a material known in the art.

The emission layer may include a host material and a dopant material. The host material includes the compound of Formula 1 herein, and may further include a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran, dibenzofuran. derivatives, dibenzothiophene, dibenzothiophene derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The dopant material includes, but is not limited to, the following compounds.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. This is suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the second electrode, an excellent electron injection effect on the light emitting layer or the light emitting material, and A compound which prevents migration to the hole injection layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The hole blocking layer is a layer that blocks holes from reaching the second electrode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for illustrating the present specification, and not for limiting the present specification.

The compound according to the present specification was prepared using the Buchwald-Hartwig coupling reaction, the Heck coupling reaction, the Suzuki coupling reaction, etc. as representative reactions.

[Preparation Example 1] Preparation of formula a (5H-benzo [b] carbazole)

1) Preparation of Formula a-1

Naphthalen-2-amine 300.0 g (1.0 eq), 1-bromo-2-iodobenzene 592.7 g (1.0 eq), NaOtBu 302.0 g (1.5 eq), palladium acetate (Pd(OAc) ₂ ) 4.70 g (0.01 eq), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (4,5-Bis(diphenylphosphino)-9,9 -dimethylxanthene, Xantphos) 12.12 g (0.01 eq) and 1,4-dioxane (1,4-dioxane) were dissolved in 5L and stirred under reflux. When the reaction was completed after 3 hours, the solvent was removed under reduced pressure. After that, it was completely dissolved in ethyl acetate (Ethylacetate), washed with water, and again under reduced pressure to remove about 70% of the solvent. Hexane was added again under reflux, and the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain 443.5 g of compound a-1 (yield 71%). [M+H]=299

2) Preparation of formula a (5H-benzo[b]carbazole)

Formula a-1 443.5 g (1.0 eq) of Pd(t-Bu ₃ P) ₂ 8.56 g (0.01 eq), K ₂ CO ₃ 463.2 g (2.00 eq) into 4L of diethylacetamide (Dimethylacetamide, DMAC) The mixture was refluxed and stirred. After 3 hours, the reaction product was poured into water to drop crystals and filtered. The filtered solid was completely dissolved in 1,2-dichlorobenzene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to drop crystals, cooled, and filtered. This was purified by column chromatography to obtain 174.8 g of formula a (5H-benzo[b]carbazole) (yield 48%). [M+H]=218

Here, tBu means tertbutyl.

[Preparation Example 2] Preparation of formula b (7H-dibenzo[b,g]carbazole)

Using 1-bromo-2-iodonaphthalene instead of 1-bromo-2-idobenzene, formula b (7H-dibenzo[b ,g]carbazole) was synthesized.

[Preparation Example 3] Preparation of formula c(6H-dibenzo[b,h]carbazole)

Using 2,3-dibromonaphthalene instead of 1-bromo-2-idobenzene, formula c (6H-dibenzo[b,h]carbazole ) was synthesized.

[Preparation Example 4] Preparation of formula d (13H-dibenzo[a,h]carbazole)

Using 2-bromo-1-iodonaphthalene instead of 1-bromo-2-idobenzene, formula d (13H-dibenzo[a ,h]carbazole) was synthesized.

[Preparation Example 5] Preparation of formula e

1) Preparation of Formula e-2

1-bromo-4-chloro-3-fluoro-2-idobenzene (1-bromo-4-chloro-3-fluoro-2-iodobenzene) 200.0 g (1.0 eq), (2-hydroxyphenyl) Boronic acid ((2-hydroxyphenyl)boronic acid) 82.3 g (1.0 eq), K ₂ CO ₃ 164.6 g (2.0 eq) and Pd(PPh ₃ ) ₄ (Tetrakis(triphenylphosphine)palladium(0))13.77 g (0.02 eq) ) was dissolved in tetrahydrofuran (THF) 3L, refluxed and stirred. When the reaction was completed after 2 hours, the solvent was removed under reduced pressure. After that, it was completely dissolved in ethylacetate, washed with water, and again under reduced pressure to remove about 80% of the solvent. Hexane was added under reflux again, crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain 129.5 g of compound e-2 (yield 72%). [M+H]+=300

2) Preparation of Formula e-1

129.5 g (1.0 eq) of Formula e-2 and _{118.5 g (2.00 eq) of K 2} CO ₃ were put in 2L of diethylacetamide (Dimethylacetamide), and the mixture was refluxed and stirred. After 1 hour, the reaction product was poured into water to drop crystals and filtered. The filtered solid was completely dissolved in Ethylacetate, washed with water, and then the solvent was removed by reducing the pressure again to 70%. Hexane was added under reflux again, crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain 101.6 g of compound e-1 (yield 84%). [M+H]+=280

3) Preparation of formula e

Formula e-1 101.6 g (1.0 eq), bis(pinacolato)diboron (Bis(pinacolato)diboron) 119.1 g (1.3 eq) in Pd(dppf)Cl ₂ ((1,1'-Bis(diphenylphosphino) ferrocene)palladium dichloride)5.28 g (0.02 eq) and KOAc (potassium acetate) 40.4 g (2.00 eq) were added to dioxnae 2L, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed under reduced pressure. The filtered solid _{was completely dissolved in CHCl 3} , washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to remove about 90% of the solvent. Ethanol was added again under reflux to drop crystals, cooled, and filtered to obtain 103.1 g of formula e (yield 87%). [M+H]+=329

[Preparation Example 6] Preparation of Formula f

1-bromo-5-chloro-3-fluoro-2-iodobenzene instead of 1-bromo-4-chloro-3-fluoro-2-idobenzene (1-bromo-5-chloro-3- fluoro-2-iodobenzene) was used, and the following formula f was synthesized in the same manner as in the preparation method of formula e. [M+H]+=329

[Preparation Example 7] Preparation of formula g

2-bromo-1-chloro-4-fluoro-3-iodobenzene instead of 1-bromo-4-chloro-3-fluoro-2-idobenzene (2-bromo-1-chloro-4- fluoro-3-iodobenzene) was used to synthesize the following Chemical Formula g in the same manner as in the preparation method of Chemical Formula e. [M+H]+=329

[Preparation Example 8] Preparation of Formula h

Formula e using (3-hydroxynaphthalen-2-yl)boronic acid instead of (2-hydroxyphenyl)boronic acid The following formula h was synthesized in the same manner as in the preparation method. [M+H]+=379

[Preparation Example 9] Preparation of Formula i

Formula f using (3-hydroxynaphthalen-2-yl)boronic acid instead of (2-hydroxyphenyl)boronic acid The following formula (i) was synthesized in the same manner as in the preparation method. [M+H]+=379

[Preparation Example 10] Preparation of Formula j

Using (3-hydroxynaphthalen-2-yl)boronic acid instead of (2-hydroxyphenyl)boronic acid, the following formula j was synthesized. [M+H]+=379

[Preparation Example 11] Preparation of formula k

Using (1-hydroxynaphthalen-2-yl)boronic acid ((1-hydroxynaphthalen-2-yl)boronic acid) instead of (2-hydroxyphenyl)boronic acid, the following formula k was synthesized. [M+H]+=379

[Preparation Example 12] Preparation of Formula 1

(2-hydroxyphenyl) boronic acid instead of (1-hydroxynaphthalen-2-yl) boronic acid ((1-hydroxynaphthalen-2-yl) boronic acid) using the same method as the preparation method of formula f l was synthesized. [M+H]+=379

[Preparation Example 13] Preparation of formula m

Using (1-hydroxynaphthalen-2-yl)boronic acid instead of (2-hydroxyphenyl)boronic acid, the following formula m was synthesized. [M+H]+=379

[Preparation Example 14] Preparation of Formula n

2-bromo-1-chloro-4-fluoro-3-iodonaphthalene instead of 1-bromo-4-chloro-3-fluoro-2-idobenzene (2-bromo-1-chloro-4- Using fluoro-3-iodonaphthalene), the following formula n was synthesized in the same manner as in the preparation method of formula e. [M+H]+=379

[Preparation Example 15] Preparation of Formula o

1-bromo-4-chloro-3-fluoro-2-iodonaphthalene instead of 1-bromo-4-chloro-3-fluoro-2-idobenzene (1-bromo-4-chloro-3- Using fluoro-2-iodonaphthalene), the following formula o was synthesized in the same manner as in the preparation method of formula e. [M+H]+=379

By using the intermediate synthesized in Preparation Examples 1 to 15, the intermediate containing triazine was processed through Suzuki coupling reaction, and the compounds of the following synthesis examples were synthesized.

[Synthesis Example 1]

Intermediate 1 (10 g, 20.7 mmol) and Formula a (4.5 g, 20.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. After that, sodium tert-butoxide (NaOtBu) (6 g, 62mmol) was added and sufficiently stirred, bis(tritertiary-butylphosphine)palladium (Pd(t-Bu ₃ P) ₂ ) (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound compound 1 (8.2 g, 60%, MS: [M+H] + = 665.8).

[Synthesis Example 2]

In a nitrogen atmosphere, Intermediate 2 (10 g, 23 mmol) and Formula a (5 g, 23 mmol) were placed in 200 ml of xylene, stirred and refluxed. Thereafter, sodium tertiary-butoxide (6.6 g, 69.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.5 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound compound 2 (9.9 g, 70%, MS: [M+H] + = 615.2).

[Synthesis Example 3]

Intermediate 3 (10 g, 19.1 mmol) and Formula a (4.1 g, 19.1 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (5.5 g, 57.3 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 3 (9.3 g, 69%, MS: [M+H] + = 705.2).

[Synthesis Example 4]

Intermediate 4 (10 g, 15.9 mmol) and Formula a (3.4 g, 15.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (4.6 g, 47.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 4 (8.7 g, 68%, MS: [M+H] + = 811.2).

[Synthesis Example 5]

Intermediate 5 (10 g, 23 mmol) and Formula a (5 g, 23 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (6.6 g, 69.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 5 (8.5 g, 60%, MS: [M+H] + = 615.2).

[Synthesis Example 6]

Intermediate 6 (10 g, 17.9 mmol) and Formula a (3.9 g, 17.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (5.1 g, 53.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 6 (8.3 g, 63%, MS: [M+H] + = 741.3).

[Synthesis Example 7]

Intermediate 7 (10 g, 18.5 mmol) and Formula a (4 g, 18.5 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (5.3 g, 55.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 7 (8.7 g, 65%, MS: [M+H] + = 721.2).

[Synthesis Example 8]

Intermediate 8 (10 g, 16.7 mmol) and Formula a (3.6 g, 16.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. After that, sodium tertiary-butoxide (4.8 g, 50.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 8 (8.2 g, 63%, MS: [M+H] + = 780.3).

[Synthesis Example 9]

Intermediate 9 (10 g, 23 mmol) and Formula a (5 g, 23 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. After that, sodium tertiary-butoxide (6.6 g, 69.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.5 mmol) was added. After reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 9 (9.1 g, 64%, MS: [M+H]+ = 615.2).

[Synthesis Example 10]

Intermediate 10 (10 g, 18.7 mmol) and Formula a (4.1 g, 18.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.4 g, 56.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 10 (7.9 g, 59%, MS: [M+H] + = 715.2).

[Synthesis Example 11]

Intermediate 11 (10 g, 18.7 mmol) and Formula a (4.1 g, 18.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.4 g, 56.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 11 (8.6 g, 64%, MS: [M+H] + = 715.2).

[Synthesis Example 12]

Intermediate 12 (10 g, 16.3 mmol) and Formula a (3.5 g, 16.3 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (4.7 g, 48.9 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound compound 12 (8.9 g, 69%, MS: [M+H]+ = 795.2).

[Synthesis Example 13]

Intermediate 13 (10 g, 16.7 mmol) and Formula a (3.6 g, 16.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (4.8 g, 50.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 13 (8.6 g, 66%, MS: [M+H] + = 780.3).

[Synthesis Example 14]

Intermediate 14 (10 g, 20.7 mmol) and formula a (4.5 g, 20.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (6 g, 62 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 14 (9.1 g, 66%, MS: [M+H] + = 665.2).

[Synthesis Example 15]

Intermediate 15 (10 g, 16.9 mmol) and Formula a (3.7 g, 16.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (4.9 g, 50.8 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 15 (8.4 g, 64%, MS: [M+H] + = 771.2).

[Synthesis Example 16]

Intermediate 16 (10 g, 18.7 mmol) and Formula a (4.1 g, 18.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.4 g, 56.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 16 (7.8 g, 58%, MS: [M+H] + = 715.2).

[Synthesis Example 17]

Intermediate 17 (10 g, 15.7 mmol) and formula a (3.4 g, 15.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. After that, sodium tert-butoxide (4.5 g, 47.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 17 (7.6 g, 59%, MS: [M+H] + = 817.3).

[Synthesis Example 18]

Intermediate 18 (10 g, 20.7 mmol) and Formula a (4.5 g, 20.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (6 g, 62 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 18 (7.8 g, 57%, MS: [M+H] + = 665.2).

[Synthesis Example 19]

Intermediate 19 (10 g, 18.7 mmol) and Formula a (4.1 g, 18.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.4 g, 56.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 19 (8.7 g, 65%, MS: [M+H] + = 715.2).

[Synthesis Example 20]

Intermediate 20 (10 g, 15.4 mmol) and Formula a (3.3 g, 15.4 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.4 g, 46.1 mmol) was added, and after sufficient stirring, bis (tri tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound compound 20 (7.7 g, 60%, MS: [M+H]+ = 831.3).

[Synthesis Example 21]

Intermediate 21 (10 g, 15.7 mmol) and Formula a (3.4 g, 15.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. After that, sodium tert-butoxide (4.5 g, 47.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 21 (7.3 g, 57%, MS: [M+H] + = 817.3).

[Synthesis Example 22]

Intermediate 22 (10 g, 15.6 mmol) and Formula a (3.4 g, 15.6 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.5 g, 46.9 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 22 (8.2 g, 64%, MS: [M+H] + = 821.2).

[Synthesis Example 23]

Intermediate 23 (10 g, 17.9 mmol) and Formula b (4.8 g, 17.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.1 g, 53.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 23 (7.8 g, 55%, MS: [M+H] + = 791.3).

[Synthesis Example 24]

Intermediate 24 (10 g, 17.1 mmol) and Formula b (4.6 g, 17.1 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.9 g, 51.4 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 24 (8.8 g, 63%, MS: [M+H] + = 815.3).

[Synthesis Example 25]

Intermediate 25 (10 g, 15.4 mmol) and formula b (4.1 g, 15.4 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.4 g, 46.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 25 (7.6 g, 56%, MS: [M+H] + = 880.3).

[Synthesis Example 26]

Intermediate 26 (10 g, 19.6 mmol) and formula b (5.2 g, 19.6 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (5.7 g, 58.8 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 26 (9.4 g, 65%, MS: [M+H] + = 741.3).

[Synthesis Example 27]

Intermediate 27 (10 g, 16.3 mmol) and Formula b (4.4 g, 16.3 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (4.7 g, 48.9 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 27 (8.5 g, 62%, MS: [M+H] + = 845.3).

[Synthesis Example 28]

Intermediate 28 (10 g, 14.3 mmol) and Formula b (3.8 g, 14.3 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.1 g, 42.9 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 28 (7.3 g, 55%, MS: [M+H]+ = 930.3).

[Synthesis Example 29]

Intermediate 29 (10 g, 23 mmol) and formula c (6.2 g, 23 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (6.6 g, 69.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 29 (9g, 59%, MS: [M+H]+ = 665.2).

[Synthesis Example 30]

Intermediate 30 (10 g, 20.7 mmol) and formula c (5.5 g, 20.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (6 g, 62 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 30 (10.2 g, 69%, MS: [M+H] + = 715.2).

[Synthesis Example 31]

Intermediate 31 (10 g, 17.9 mmol) and formula c (4.8 g, 17.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.1 g, 53.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 31 (8 g, 57%, MS: [M+H] + = 791.3).

[Synthesis Example 32]

Intermediate 32 (10 g, 17.4 mmol) and formula c (4.7 g, 17.4 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (5 g, 52.3 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 32 (8 g, 57%, MS: [M+H] + = 805.2).

[Synthesis Example 33]

Intermediate 33 (10 g, 23 mmol) and Formula c (6.2 g, 23 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (6.6 g, 69.1 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.5 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 33 (10.4 g, 68%, MS: [M+H] + = 665.2).

[Synthesis Example 34]

Intermediate 34 (10 g, 17.9 mmol) and formula c (4.8 g, 17.9 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.1 g, 53.6 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 34 (9g, 64%, MS: [M+H]+ = 791.9).

[Synthesis Example 35]

Intermediate 35 (10 g, 19.1 mmol) and formula c (5.1 g, 19.1 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tert-butoxide (5.5 g, 57.4 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 35 (9.9 g, 69%, MS: [M+H] + = 754.3).

[Synthesis Example 36]

Intermediate 36 (10 g, 19.1 mmol) and Formula d (5.1 g, 19.1 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (5.5 g, 57.4 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 36 (9.9 g, 69%, MS: [M+H] + = 754.3).

[Synthesis Example 37]

Intermediate 37 (10 g, 16.2 mmol) and formula d (4.3 g, 16.2 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.7 g, 48.7 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 37 (8.1 g, 59%, MS: [M+H] + = 847.3).

[Synthesis Example 38]

Intermediate 38 (10 g, 16.2 mmol) and formula d (4.3 g, 16.2 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. Thereafter, sodium tertiary-butoxide (4.7 g, 48.7 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 38 (7.7 g, 56%, MS: [M+H] + = 847.3).

[Synthesis Example 39]

Intermediate 39 (10 g, 16.7 mmol) and formula d (4.5 g, 16.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, and stirred and refluxed. After that, sodium tertiary-butoxide (4.8 g, 50.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 39 (8 g, 58%, MS: [M+H] + = 830.3).

[Synthesis Example 40]

Intermediate 40 (10 g, 20.7 mmol) and Formula a (4.5 g, 20.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (6 g, 62 mmol) was added thereto, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added thereto. After reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 40 (8.5 g, 62%, MS: [M+H] + = 665.2).

[Synthesis Example 41]

Intermediate 41 (10 g, 17.4 mmol) and Formula a (3.8 g, 17.4 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tert-butoxide (5 g, 52.3 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.3 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 41 (8.3 g, 63%, MS: [M+H] + = 755.2).

[Synthesis Example 42]

Intermediate 42 (10 g, 18.7 mmol) and formula c (5 g, 18.7 mmol) were placed in 200 ml of xylene under a nitrogen atmosphere, stirred and refluxed. Thereafter, sodium tertiary-butoxide (5.4 g, 56.2 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.2 g, 0.4 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in chloroform to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 42 (9.3 g, 65%, MS: [M+H] + = 765.3).

[Comparative Example 1]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The following HI-1 compound was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following A-1 compound was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following EB-1 compound was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, the following RH-1 compound and the following Dp-7 compound were vacuum-deposited in a weight ratio of 98:2 on the EB-1 deposited layer to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic material was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3Å/sec, and the deposition rate of aluminum was maintained at 2Å/sec, and the vacuum degree during deposition was 2×10 ^{- An} organic light-emitting device was manufactured by maintaining 7 to 5×10 ^{-6 torr.}

[Examples 1 to 42]

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of RH-1 in the organic light emitting device of Comparative Example 1.

[Comparative Examples 2 to 13]

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of RH-1 in the organic light emitting device of Comparative Example 1.

When a current was applied to the organic light emitting diodes prepared in Examples 1 to 42 and Comparative Examples 1 to 13, voltage, efficiency, and lifetime were measured (based on 6000 nits), and the results are shown in Table 1 below. . The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

division matter Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Comparative Example 1 RH-1 4.34 38.3 193 Red Example 1 compound 1 3.61 44.5 241 Red Example 2 compound 2 3.63 43.7 250 Red Example 3 compound 3 3.69 44.8 247 Red Example 4 compound 4 3.62 44.1 258 Red Example 5 compound 5 3.74 44.5 306 Red Example 6 compound 6 3.77 44.3 301 Red Example 7 compound 7 3.72 42.9 298 Red Example 8 compound 8 3.71 44.5 307 Red Example 9 compound 9 3.50 47.3 293 Red Example 10 compound 10 3.55 47.1 292 Red Example 11 compound 11 3.53 47.8 287 Red Example 12 compound 12 3.51 47.3 299 Red Example 13 compound 13 3.54 47.9 285 Red Example 14 compound 14 3.49 45.1 267 Red Example 15 compound 15 3.51 45.0 264 Red Example 16 compound 16 3.63 45.2 257 Red Example 17 compound 17 3.58 44.6 319 Red Example 18 compound 18 3.43 43.9 313 Red Example 19 compound 19 3.52 49.1 303 Red Example 20 compound 20 3.38 45.5 254 Red Example 21 compound 21 3.63 49.6 304 Red Example 22 compound 22 3.51 44.3 315 Red Example 23 compound 23 3.57 45.7 261 Red Example 24 compound 24 3.39 45.2 267 Red Example 25 compound 25 3.40 46.3 314 Red Example 26 compound 26 3.42 48.8 297 Red Example 27 compound 27 3.51 49.1 305 Red Example 28 compound 28 3.38 49.8 303 Red Example 29 compound 29 3.54 49.1 329 Red Example 30 compound 30 3.52 51.8 304 Red Example 31 compound 31 3.33 49.3 291 Red Example 32 compound 32 3.57 49.4 299 Red Example 33 compound 33 3.52 49.8 308 Red Example 34 compound 34 3.43 47.3 306 Red Example 35 compound 35 3.51 49.7 301 Red Example 36 compound 36 3.47 47.9 297 Red Example 37 compound 37 3.54 47.3 318 Red Example 38 compound 38 3.43 48.0 308 Red Example 39 compound 39 3.49 48.7 297 Red Example 40 compound 40 3.47 49.5 285 Red Example 41 compound 41 3.46 49.3 279 Red Example 42 compound 42 3.45 49.0 297 Red Comparative Example 2 C-1 4.13 37.2 131 Red Comparative Example 3 C-2 4.81 34.1 140 Red Comparative Example 4 C-3 4.30 35.1 167 Red Comparative Example 5 C-4 4.68 33.0 79 Red Comparative Example 6 C-5 4.41 32.4 97 Red Comparative Example 7 C-6 4.77 29.7 61 Red Comparative Example 8 C-7 4.21 34.0 103 Red Comparative Example 9 C-8 4.19 35.7 114 Red Comparative Example 10 C-9 4.71 31.3 73 Red Comparative Example 11 C-10 4.19 35.7 114 Red Comparative Example 12 C-11 4.71 31.3 73 Red Comparative Example 13 C-12 4.71 31.3 73 Red

When a current was applied to the organic light emitting diodes fabricated in Examples 1 to 42 and Comparative Examples 1 to 13, the results shown in Table 1 were obtained. The red organic light emitting device of Comparative Example 1 used a material widely used in the prior art, and has a structure using compound [EB-1] as an electron blocking layer and RH-1/Dp-7 as a red light emitting layer. In Comparative Examples 2 to 13, organic light emitting devices were manufactured using C-1 to C-12 instead of RH-1.

Looking at the results in Table 1, when the compound of the present invention is used as a host of the red light emitting layer, the driving voltage is largely lowered by nearly 30% compared to the comparative example material, and in terms of efficiency, it is seen that the red plate in the host is increased by 25% or more. It was found that the energy transfer to Troy was well performed. In addition, it was found that the lifespan characteristics could be greatly improved more than twice while maintaining high efficiency. It can be determined that this is because the compound of the present invention has higher stability to electrons and holes than the compound of Comparative Example.

[Examples 43 to 142]

In the organic light emitting device of Comparative Example 1, instead of RH-1, the first host and the second host shown in Table 1 were vacuum co-deposited in a 1:1 weight ratio, and organic light emission was performed in the same manner as in Comparative Example 1, except for this. The device was manufactured, and the device performance was evaluated in the same manner as in Table 1, and is shown in Tables 2 and 3.

division 1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 43 compound 2 Z-1 3.65 45.2 402 Red Example 44 Z-4 3.68 44.9 411 Red Example 45 Z-10 3.69 46.0 408 Red Example 46 Z-13 3.68 44.2 423 Red Example 47 Z-21 3.65 43.9 417 Red Example 48 Z-25 3.67 44.1 408 Red Example 49 Z-31 3.70 45.3 421 Red Example 50 Z-33 3.68 44.0 417 Red Example 51 compound 5 Z-1 3.79 45.5 465 Red Example 52 Z-4 3.78 45.8 469 Red Example 53 Z-10 3.82 46.9 458 Red Example 54 Z-13 3.78 44.5 461 Red Example 55 Z-21 3.83 45.7 454 Red Example 56 Z-25 3.80 45.9 451 Red Example 57 Z-31 3.82 45.2 467 Red Example 58 Z-33 3.77 44.8 462 Red Example 59 compound 9 Z-1 3.58 47.6 453 Red Example 60 Z-4 3.57 47.9 451 Red Example 61 Z-10 3.59 48.1 449 Red Example 62 Z-13 3.55 47.8 467 Red Example 63 Z-21 3.61 47.5 452 Red Example 64 Z-25 3.59 48.9 461 Red Example 65 Z-31 3.62 47.9 468 Red Example 66 Z-33 3.58 48.0 455 Red Example 67 compound 16 Z-2 3.69 46.2 427 Red Example 68 Z-7 3.68 45.9 3.97 Red Example 69 Z-11 3.70 45.9 419 Red Example 70 Z-15 3.68 45.7 410 Red Example 71 Z-18 3.67 46.5 391 Red Example 72 Z-19 3.71 45.8 415 Red Example 73 Z-22 3.69 45.7 493 Red Example 74 Z-23 3.70 45.9 395 Red Example 75 Z-27 3.72 46.7 411 Red Example 76 Z-34 3.68 45.8 498 Red Example 77 compound 18 Z-2 3.49 45.9 461 Red Example 78 Z-7 3.48 44.3 472 Red Example 79 Z-11 3.49 44.8 462 Red Example 80 Z-15 3.51 44.5 454 Red Example 81 Z-18 3.45 45.3 458 Red Example 82 Z-19 3.48 44.7 449 Red Example 83 Z-22 3.52 45.9 486 Red Example 84 Z-23 3.50 46.4 467 Red Example 85 Z-27 3.47 44.5 466 Red Example 86 Z-34 3.49 46.0 458 Red Example 87 compound 26 Z-2 3.49 50.0 462 Red Example 88 Z-7 3.47 49.3 481 Red Example 89 Z-11 3.52 49.4 473 Red Example 90 Z-15 3.49 49.9 462 Red Example 91 Z-18 3.47 50.5 468 Red Example 92 Z-19 3.46 49.7 477 Red Example 93 Z-22 3.50 49.5 486 Red Example 94 Z-23 3.48 50.3 471 Red Example 95 Z-27 3.51 49.7 469 Red Example 96 Z-34 3.53 50.5 473 Red Example 97 compound 28 Z-2 3.48 50.5 461 Red Example 98 Z-7 3.45 51.6 457 Red Example 99 Z-11 3.40 51.7 449 Red Example 100 Z-15 3.49 51.1 468 Red Example 101 Z-18 3.51 50.7 471 Red Example 102 Z-19 3.43 51.4 466 Red Example 103 Z-22 3.47 50.6 481 Red Example 104 Z-23 3.44 50.9 458 Red Example 105 Z-27 3.49 52.1 467 Red Example 106 Z-34 3.50 51.4 463 Red Example 107 compound 32 Z-3 3.61 51.3 461 Red Example 108 Z-8 3.63 50.8 475 Red Example 109 Z-12 3.61 52.7 454 Red Example 110 Z-16 3.60 51.5 460 Red Example 111 Z-20 3.67 51.8 447 Red Example 112 Z-29 3.64 51.6 476 Red Example 113 Z-30 3.61 52.0 440 Red Example 114 Z-32 3.65 50.6 479 Red Example 115 compound 33 Z-3 3.62 51.0 481 Red Example 116 Z-8 3.69 52.7 498 Red Example 117 Z-12 3.58 51.2 470 Red Example 118 Z-16 3.54 51.4 467 Red Example 119 Z-20 3.59 51.9 465 Red Example 120 Z-29 3.58 52.3 443 Red Example 121 Z-30 3.60 50.9 465 Red Example 122 Z-32 3.58 53.3 473 Red

division 1st host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 123 compound 38 Z-5 3.49 49.6 431 Red Example 124 Z-6 3.48 49.7 438 Red Example 125 Z-9 3.49 50.1 405 Red Example 126 Z-14 3.46 49.5 418 Red Example 127 Z-17 3.51 51.6 438 Red Example 128 Z-24 3.49 50.3 429 Red Example 129 Z-26 3.47 49.2 437 Red Example 130 Z-28 3.52 48.8 458 Red Example 131 Z-35 3.50 51.9 451 Red Example 132 Z-36 3.48 48.7 455 Red Example 133 compound 41 Z-5 3.49 50.5 399 Red Example 134 Z-6 3.51 51.3 401 Red Example 135 Z-9 3.49 50.8 388 Red Example 136 Z-14 3.53 49.7 379 Red Example 137 Z-17 3.55 52.0 412 Red Example 138 Z-24 3.59 51.3 388 Red Example 139 Z-26 3.49 50.8 403 Red Example 140 Z-28 3.53 51.7 389 Red Example 141 Z-35 3.50 52.3 393 Red Example 142 Z-36 3.56 50.3 387 Red

The results in Tables 2 and 3 show the results of co-deposition of two types of hosts. When the first host and the second host were used in a 1:1 ratio, better results were obtained than the result of using only the first host. As the amount of holes increases as the second host is used, electrons and holes in the red light emitting layer maintain a more stable balance, and it can be seen that efficiency and lifespan are greatly increased.

In conclusion, it was confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting device could be improved when the compound of the present invention was used as a host for the red light emitting layer.

1: Substrate
2: first electrode
3: light emitting layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: Electronic blocking layer
8: hole blocking layer
9: Electron injection and transport layer

Claims (14)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R1 is hydrogen; or deuterium,
R2 to R4 are each independently hydrogen; or deuterium, or adjacent substituents combine with each other to form a substituted or unsubstituted benzene ring,
R5 and R6 are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a is an integer from 0 to 6,
b and d are each independently an integer of 0 to 4,
c is an integer from 0 to 2,
a to d are each independently, when two or more, the substituents in parentheses are the same as or different from each other. The method according to claim 1, wherein the compound represented by Formula 1 is a compound selected from any one of the following Formulas 2 to 4:
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, R1 to R6 and a to d are as defined in Formula 1. The method according to claim 1, wherein the compound represented by Formula 1 is a compound selected from any one of the following Formulas 2-1 to 2-8:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

In Formulas 2-1 to 2-8, R4 to R6 and d are as defined in Formula 1,
R7 is hydrogen; or deuterium,
e1 and e2 are each 0 or 1, the sum of e1 and e2 is 1 to 2,
e is an integer from 0 to 10,
When e is 2 or more, a plurality of R7s are the same as or different from each other. The compound according to claim 1, wherein the compound represented by Formula 1 is selected from any one of the following Formulas 3-1 to 3-8:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

In Formulas 3-1 to 3-8, R4 to R6 and d are as defined in Formula 1,
R8 is hydrogen; or deuterium,
f is an integer from 0 to 8;
When f is 2 or more, a plurality of R8s are the same as or different from each other. The method according to claim 1, wherein the compound represented by Formula 1 is a compound selected from any one of the following Formulas 4-1 to 4-8:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

In Formulas 4-1 to 4-8, R4 to R6 and d are as defined in Formula 1,
R7 is hydrogen; or deuterium,
e1 and e2 are each 0 or 1, the sum of e1 and e2 is 1 to 2,
e is an integer from 0 to 10,
When e is 2 or more, a plurality of R7s are the same as or different from each other. The method according to claim 1,
The compound represented by Formula 1 is a compound selected from the following compounds:

. a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode,
At least one of the organic material layers is an organic light-emitting device comprising the compound according to any one of claims 1 to 6. 8. The method of claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer is an organic light emitting device comprising the compound of Formula 1. 8. The method of claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer is an organic light emitting device comprising the compound of Formula 1 as a host. 8. The method of claim 7,
The organic layer includes a hole injection layer or a hole transport layer,
The hole injection layer or the hole transport layer is an organic light emitting device comprising the compound of Formula 1. 8. The method of claim 7,
The organic layer includes an electron transport layer or an electron injection layer,
The electron transport layer or the electron injection layer is an organic light emitting device comprising the compound of Formula 1. 8. The method of claim 7,
The organic light emitting device further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. 8. The method of claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer includes the compound of Formula 1 as a first host, and an organic light emitting device further comprising a second host represented by the following Formula H:
[Formula H]

In the above formula (H),
A is a substituted or unsubstituted naphthalene ring,
Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,
L1 to L3 are each independently, a single bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,
Ar2 and Ar3 are each independently, a substituted or unsubstituted C6-C60 aryl group; Or a C 2 to C 60 heteroaryl group containing at least one heteroatom among substituted or unsubstituted N, O and S,
p is an integer from 0 to 9; 14. The method of claim 13,
The second host represented by the formula (H) is an organic light emitting device represented by any one of the following structures:

.

Images